EP3184508A1 - Low temperature radical initiator system and processes making use thereof - Google Patents
Low temperature radical initiator system and processes making use thereof Download PDFInfo
- Publication number
- EP3184508A1 EP3184508A1 EP15202134.1A EP15202134A EP3184508A1 EP 3184508 A1 EP3184508 A1 EP 3184508A1 EP 15202134 A EP15202134 A EP 15202134A EP 3184508 A1 EP3184508 A1 EP 3184508A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- acid
- reactions
- alkyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000003999 initiator Substances 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title claims abstract description 41
- 239000003377 acid catalyst Substances 0.000 claims abstract description 28
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims abstract description 6
- 150000002978 peroxides Chemical class 0.000 claims description 70
- -1 silyloxyl Chemical group 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 50
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 28
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 26
- 125000001072 heteroaryl group Chemical group 0.000 claims description 26
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 26
- 125000003342 alkenyl group Chemical group 0.000 claims description 25
- 125000000304 alkynyl group Chemical group 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 230000000977 initiatory effect Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 19
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 12
- 238000010526 radical polymerization reaction Methods 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 9
- 238000007348 radical reaction Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007342 radical addition reaction Methods 0.000 claims description 7
- 238000006596 Alder-ene reaction Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006734 Wohl-Ziegler bromination reaction Methods 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 150000008360 acrylonitriles Chemical class 0.000 claims description 5
- 230000003412 degenerative effect Effects 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 238000006476 reductive cyclization reaction Methods 0.000 claims description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003926 acrylamides Chemical class 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000003440 styrenes Chemical class 0.000 claims description 4
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical group [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- FFTQWJGHWSSCDA-UHFFFAOYSA-K FC(S(=O)(=O)[O-])(F)F.[Hf+3].FC(S(=O)(=O)[O-])(F)F.FC(S(=O)(=O)[O-])(F)F Chemical compound FC(S(=O)(=O)[O-])(F)F.[Hf+3].FC(S(=O)(=O)[O-])(F)F.FC(S(=O)(=O)[O-])(F)F FFTQWJGHWSSCDA-UHFFFAOYSA-K 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 claims description 2
- UCYRAEIHXSVXPV-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)indiganyl trifluoromethanesulfonate Chemical compound [In+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F UCYRAEIHXSVXPV-UHFFFAOYSA-K 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 125000005499 phosphonyl group Chemical group 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 claims description 2
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000007792 addition Methods 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 241000894007 species Species 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000003573 thiols Chemical group 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000003818 flash chromatography Methods 0.000 description 4
- 229910052986 germanium hydride Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910052990 silicon hydride Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 4
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- SCHZCUMIENIQMY-UHFFFAOYSA-N tris(trimethylsilyl)silicon Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)[Si](C)(C)C SCHZCUMIENIQMY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000001502 aryl halides Chemical class 0.000 description 3
- 238000010504 bond cleavage reaction Methods 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- FPCCSQOGAWCVBH-UHFFFAOYSA-N ketanserin Chemical compound C1=CC(F)=CC=C1C(=O)C1CCN(CCN2C(C3=CC=CC=C3NC2=O)=O)CC1 FPCCSQOGAWCVBH-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- CBFIPOTVFMLMFQ-UHFFFAOYSA-N 9-iodophenanthrene Chemical compound C1=CC=C2C(I)=CC3=CC=CC=C3C2=C1 CBFIPOTVFMLMFQ-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006822 Barton-McCombie deoxygenation reaction Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001743 benzylic group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005940 1,4-dioxanyl group Chemical group 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- HLJZFZYTQCCABR-UHFFFAOYSA-N 1-bromopyrrolidine-2,5-dione;hydrobromide Chemical compound Br.BrN1C(=O)CCC1=O HLJZFZYTQCCABR-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- MARXMDRWROUXMD-UHFFFAOYSA-N 2-bromoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Br)C(=O)C2=C1 MARXMDRWROUXMD-UHFFFAOYSA-N 0.000 description 1
- WDRFYIPWHMGQPN-UHFFFAOYSA-N 2-chloroisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Cl)C(=O)C2=C1 WDRFYIPWHMGQPN-UHFFFAOYSA-N 0.000 description 1
- CFCFZJHCTNKHGJ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)C(O)=O CFCFZJHCTNKHGJ-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004485 2-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical compound [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 1
- 125000004539 5-benzimidazolyl group Chemical group N1=CNC2=C1C=CC(=C2)* 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- 238000006611 Barton decarboxylation reaction Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000012987 RAFT agent Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000007874 V-70 Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000001504 aryl thiols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KJISMKWTHPWHFV-UHFFFAOYSA-N ethyl(dimethyl)silicon Chemical compound CC[Si](C)C KJISMKWTHPWHFV-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000006342 heptafluoro i-propyl group Chemical group FC(F)(F)C(F)(*)C(F)(F)F 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000004312 morpholin-2-yl group Chemical group [H]N1C([H])([H])C([H])([H])OC([H])(*)C1([H])[H] 0.000 description 1
- 125000004572 morpholin-3-yl group Chemical group N1C(COCC1)* 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- CJYQZTZSYREQBD-UHFFFAOYSA-N n-fluorobenzenesulfonamide Chemical compound FNS(=O)(=O)C1=CC=CC=C1 CJYQZTZSYREQBD-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 description 1
- 238000006025 oxidative dimerization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004483 piperidin-3-yl group Chemical group N1CC(CCC1)* 0.000 description 1
- 125000004482 piperidin-4-yl group Chemical group N1CCC(CC1)* 0.000 description 1
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 125000006513 pyridinyl methyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 125000004943 pyrimidin-6-yl group Chemical group N1=CN=CC=C1* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/20—Peroxy compounds the —O—O— group being bound to a carbon atom further substituted by singly—bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/20—Peroxy compounds the —O—O— group being bound to a carbon atom further substituted by singly—bound oxygen atoms
- C07C409/22—Peroxy compounds the —O—O— group being bound to a carbon atom further substituted by singly—bound oxygen atoms having two —O—O— groups bound to the carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/40—Peroxy compounds containing nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Definitions
- the present invention refers to a process making use of an initiator system comprising certain peroxide compounds, in particular peroxyketals, in the presence of an acid catalyst to initiate radical processes at low temperature, and the initiator system.
- Radical chemistry classically relies on the use of initiators to generate free radical species by the thermal homolytic scission of weak chemical bonds.
- the generated free radical species can then initiate a variety of radical reactions that are of general interest to the chemical community, and of particular relevance to the polymer industry, but also find an increasingly large number of applications in organic synthesis.
- an initiator system, or initiator is to be understood as a chemical compound or combination of chemical compounds capable of generating initiating radical species under relevant experimental conditions.
- An overview of classical initiator systems can be found in " Lalevée, J. and Fouassier, J. P. 2012. Overview of Radical Initiation. Encyclopedia of Radicals in Chemistry, Biology and Materials ".
- the most represented class of initiators are peroxide compounds, wherein a weak O-O bond is broken to generate free radicals, and azobis compounds, wherein two carbon-centered radicals are generated by the release of nitrogen gas, both reactions relying on thermal decomposition by homolytic bond cleavage of weak chemical bonds. Examples of classically used thermal initiators are shown in Scheme 1, along with their 10 hours half-life temperature. Because these compounds undergo thermal decomposition to generate the reactive radical species, radical processes are usually carried out at elevated temperature, i.e. above 70°C.
- an initiator that decomposes at such temperatures with a sufficient rate.
- the desired initiator therefore has to be sufficiently unstable to decompose at relatively low temperature but needs to be stable enough to be produced, transported and handled without requiring extreme precautions.
- Two examples of such commercially available low temperature initiators are cumyl peroxyneodecanoate and the azobis compound V-70 which have 10 hour half-life temperatures of only 38°C and 30°C, respectively. While these are commercial and useful products, it is evident that such compounds are extremely hazardous, as illustrated by their respective Self Accelerating Decomposition Temperature (SADT) of 10°C and 30°C. Particular care therefore has to be taken during their production, handling and storage.
- SADT Self Accelerating Decomposition Temperature
- Peroxyketals are well-known initiators in the context of polymer chemistry, for example in the curing of unsaturated polyester resins, and a variety of them are commercially available.
- U.S. Patent No. 4,032,596 describes the combination of a perketal and quaternary ammonium salts for the acceleration of the radical curing of polyesters. No acids were used in this invention and the ammonium salt addition was for reducing the curing time at the reaction temperature of around 100°C.
- Sheppard and Kamath are mentioning the combination of a perketal and dichloroacetic acid for the radical curing of resins.
- the acid addition was intended for reducing the curing time at the reaction temperature of about 132°C.
- U.S. Patent No. 4,376,841 describes the combination of geminal bisperoxides (perketals) and an acid or acid-releasing compound for the copolymerization of unsaturated polyester resins to generate undefined crosslinked polymers.
- free radicals can be easily and reliably generated by the combination of a certain type of organic peroxides and an acid catalyst. These radicals can then initiate radical processes at temperatures well below those needed to induce free radical formation thermally (by homolytic O-O bond cleavage) from these organic peroxides, for example at 0°C.
- a free radical is defined, following the IUPAC definition, as a chemical entity having an unpaired electron and is not to be confused with the term radical often used to describe substituents on complex molecules.
- a radical process or reaction is defined as a process or reaction involving or making use of free radicals as reaction intermediates or initiating species.
- an initiator system, or initiator is to be understood as a chemical compound or combination of chemical compounds capable of generating initiating free radical species under relevant experimental conditions.
- the present invention is directed to a process for carrying out a chemical radical reaction in which an initiator system capable of generating a radical species for initiating a variety of radical reactions at low temperature is used.
- the present invention refers to a process for carrying out a chemical reaction in which a compound capable of forming a chemical radical is reacted with a reaction partner in a radical reaction in the presence of said initiator system comprising at least an acid, preferably selected from a Broensted acid or a Lewis acid, and a compound of the general formula (I) as detailed below.
- Said chemical reactions include, but are not limited to:
- the initiator system comprises at least two components: a peroxide and an acid catalyst.
- the peroxide component has the general Formula (I): wherein:
- R S1 R S2 and R S3 each individually represent H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, sulfonyl, silyl, each being optionally substituted by one or more alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl, sulfonyl or heterosubstituent.
- any two of R, R 1 , R 2 , R 3 , R 4 , R 5 , R S1 R S2 and R S3 together form a ring structure comprising 3 to 20 ring atoms which may further be substituted by alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent or include heteroatoms, including peroxygroup(s), within the cyclic structure.
- R 1 , R 2 , R 3 , R 4 , R 5 , R S1 R S2 and R S3 may be bound to a soluble polymer or a solid phase material, such as a polymeric or inorganic support.
- the peroxide component of the general formula (I) comprises at least one peroxyketal group as represented in the general formula (I) wherein X is OOR 1 and R 1 to R 5 have the same meaning as given before.
- alkyl may be C 1 -C 20 -Alkyl which can be straight chain or branched or cyclic and has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
- Alkyl might particularly be C 1 -C 6 -alkyl, in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, likewise pentyl, 1-, 2- or 3-methylpropyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-, 2-, 3- or 4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl, 1- or 2-ethylbutyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1,1,2- or 1,2,2-trimethylpropyl.
- Substituted alkyl groups can be for example trifluoromethyl, pentafluoroethyl and 1,1,1-trifluoroethyl.
- Cycloalkyl may be a cyclic alkyl group forming a 3 to 10 membered ring and might be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
- Heterocycloalkyl may be a cycloalkyl forming a 3 to 10 membered ring and incorporating one or more heteroatoms selected from N, O, S and Si within the cycle.
- heterocycloalkyls can be preferentially selected from 2,3-dihydro-2-, -3-, -4- or -5-furyl, 2,5-dihydro-2-, -3-, -4- or -5-furyl, tetrahydro-2- or -3-furyl, 1,3-dioxolan-4-yl, tetrahydro-2- or -3-thienyl, 2,3-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl, 2,5-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl, 1-, 2- or 3-pyrrolidinyl, tetrahydro-1-, -2- or -4-imi
- Alkenyl might be C 2 -C 20 alkenyl.
- Alkynyl might be C 2 -C 20 alkynyl.
- Halogen is F, Cl , Br or I.
- Aryl might be phenyl, naphthyl or biphenyl and substituted derivatives thereof.
- Aralkyl might be benzyl, naphthylmethyl and substituted derivatives thereof.
- Heteroaryl may have one or more heteroatoms selected from N, O ,S and Si and is preferably 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4-or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, also preferably 1,2,3-triazol-1-, -4- or -5-yl, 1,2,4-triazol-1-, -3- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thi
- Heteroaralkyl might be any of the aforementioned heteroaryl bound to an alkyl group, such as pyridinylmethyl.
- Optionally substituted means unsubstituted or monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or even further substituted on the respective group.
- the peroxide component of the general formula (I) might be preferably selected from the group of compounds shown in Scheme 2.
- the peroxide component of the initiator system may be introduced to the reacting system in pure form, as a solution in a solvent, formed in-situ from suitable precursors before the introduction of the acid catalyst component, as an non-purified mixture, for example of components required for its formation under commercially relevant conditions, or be present in residual amounts from a previous process, for example a radical process relying on its thermal decomposition, or as a mixture of several peroxides,
- the acid catalyst component can be any compound with sufficient acidic properties.
- the acid catalyst can be an organic or mineral acid, often described as Br ⁇ nsted acids, or a metal salt with Lewis acidic properties.
- the acid catalyst component can be used under homogeneous or heterogeneous conditions.
- the acid catalyst component is completely or partially soluble in the reaction medium.
- the acid catalyst remains in a separate phase, typically a liquid or solid phase or immobilized on a support, from the reaction medium, allowing for example the recovery of the acid catalyst component at the end of the reaction, while the activation reaction occurs at the interface of these two separate phases.
- the acid catalyst can be an organic or mineral acid having a pKa value in water of 4,75 or lower.
- Such acid might be for example trifluoroacetic acid, nitric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, para-toluenesulfonic acid, phosphoric acid, trifluoromethanesulfonic acid (triflic acid), 1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (triflimide).
- the acid catalyst can be a salt of an element selected from groups 1, 2, 3, 4, 12, 13, 14 and 15 of the periodic table.
- Such acid catalyst might be for example Scandium(III) triflate, Ytterbium(III) triflate, Titanium(IV) chloride, Hafnium(III) triflate, Zinc(II) chloride, Aluminium(III) chloride, Indium(III) triflate, Tin(II) chloride, Tin(IV) chloride, Bismuth(III) triflate.
- mixtures of peroxides having different reactivities and/or mixtures of acids having different pKa value can be used in order to control the free radical reaction.
- the ratio of peroxide to acid catalyst components can vary widely from 1:100 to 100:1 depending on the particular radical process in which it is to be used.
- the ratio varies between 1:10 to 10:1.
- a 1:1 ratio is advantageously convenient.
- the amount of initiator can again widely vary depending on the particular radical process being initiated. Preferred amounts can vary from catalytic amounts, for example from 0.01 mol% to 20 mol% to overstoichiometric amounts, as high as 1000 mol%.
- solvents used in the inventive process are not particularly limited or even required and may be preferably selected from aliphatic, cycloaliphatic or aromatic solvents, chlorinated solvents, alcohols, in particular lower aliphatic alcohols, esters, ethers or mixtures thereof such as, for example, hexane, benzene, toluene, dichloromethane, chloroform, methanol, dimethylsulfoxide, acetic acid, acetonitrile, ethyl acetate or diethyl ether.
- the initiator system can also be used without any additional solvent, for example in the case of a radical polymerisation.
- the reaction temperature is in general a temperature lower than the 10 hour half-life temperature of the peroxide component of general Formula (I) used. It can therefore be generally selected from any temperature below 100°C. In a preferred embodiment, the temperature is selected between -40°C and 60°C. Typically, reactions are advantageously run between 0°C and 25°C.
- the radicals are formed from the peroxide component (24) in the presence of an acid catalyst component by the formation of an alkenyl peroxide (25), which is a generally very unstable structure that rapidly decomposes into radical (26) and an oxyl radical by O-O bond homolysis at low temperatures.
- so-generated free radicals can then be used as initiating species for many types of radical process known to those skilled in the art, including, for example, but not limited to, all as further exemplified above:
- radical processes are for example radical deoxygenations, known as the Barton-McCombie reaction; polymerisation of a wide variety of olefinic monomers, such as vinyl acetates, acrylonitriles, butadiene and the like; or the wide variety of radical chain reactions relying on metal-hydride, such as tin, germanium or silicon hydrides, or sulphur based radical transfer agents.
- the peroxides which can be used according to the invention are not particularly limited as long as they are covered by the formula (I) as represented above.
- Compounds that have been exemplarily used by the inventors are peroxides 1-11b, shown in Scheme 2. Some of these compounds as well as derivatives thereof are commercially available.
- the inventive initiator system can be particularly used as a complementary strategy to the existing radical initiators.
- Said initiator system can be used to efficiently initiate radical processes at ambient temperature, temperatures as low as -20°C or even lower. This combination has the potential to become an extremely useful and widely used system, given the commercial availability of several peroxides, their tolerance to air and moisture, their high thermal stability, compared to specifically designed low temperature initiators, and the extreme simplicity of the experimental procedure.
- the inventors selected the radical bromination of fluorene 27 by N- bromosuccinimide (NBS) at room temperature as a benchmark reaction to evaluate their inventive initiator system (Scheme 4).
- the inventive initiator system was then evaluated at cryogenic temperatures using methane sulfonic acid as a standard acid and varying the peroxide component of the initiator system.
- MMA methyl methacrylate
- radical polymerization reactions that have been conducted making use of the inventive initiator system include the synthesis of poly(n-butyl acrylate), poly(n-butyl acrylate)-b-poly(t-butyl acrylate) (a block copolymer), poly(styrene) and poly(N-isopropylacrylamide). These reactions have been carried out at ambient temperature and 0°C, respectively. These polymers have been synthesized with and without the technique of reversible addition fragmentation transfer (RAFT) polymerization.
- RAFT reversible addition fragmentation transfer
- Peroxide 1 can be efficiently used to initiate radical polymerizations when being combined with a Br ⁇ nsted acid at low temperature with any radically polymerizable vinyl monomer, such as for example styrene, butyl acrylate or N-isopropyl acrylamide. Polymers of high molecular weight are obtained in uncontrolled radical polymerizations in accordance with general expectations of such reactions. Initiation pathways have been identified and the initiating moieties do not correspond to a thermal decay of 1, but to the fragments as outlined in Scheme 4. Furthermore, 1 combined with an acid (e.g. trifluoroacetic acid) can be used to initiate also room temperature degenerative transfer polymerizations, i.e. reversible addition fragmentation radical transfer polymerization (RAFT).
- RAFT reversible addition fragmentation radical transfer polymerization
- the present invention offers a cheap, safe and user-friendly alternative to the low temperature radical initiators currently known.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
- Pyrane Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polymerization Catalysts (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention refers to a process making use of a radical initiator system comprising peroxy compounds, in particular peroxyketals, in the presence of an acid catalyst to initiate radical processes at low temperature, such as room temperature and below.
Description
- The present invention refers to a process making use of an initiator system comprising certain peroxide compounds, in particular peroxyketals, in the presence of an acid catalyst to initiate radical processes at low temperature, and the initiator system.
- Radical chemistry classically relies on the use of initiators to generate free radical species by the thermal homolytic scission of weak chemical bonds. The generated free radical species can then initiate a variety of radical reactions that are of general interest to the chemical community, and of particular relevance to the polymer industry, but also find an increasingly large number of applications in organic synthesis. In the rest of this document, an initiator system, or initiator, is to be understood as a chemical compound or combination of chemical compounds capable of generating initiating radical species under relevant experimental conditions. An overview of classical initiator systems can be found in "Lalevée, J. and Fouassier, J. P. 2012. Overview of Radical Initiation. Encyclopedia of Radicals in Chemistry, Biology and Materials".
- The most represented class of initiators are peroxide compounds, wherein a weak O-O bond is broken to generate free radicals, and azobis compounds, wherein two carbon-centered radicals are generated by the release of nitrogen gas, both reactions relying on thermal decomposition by homolytic bond cleavage of weak chemical bonds. Examples of classically used thermal initiators are shown in
Scheme 1, along with their 10 hours half-life temperature. Because these compounds undergo thermal decomposition to generate the reactive radical species, radical processes are usually carried out at elevated temperature, i.e. above 70°C. - A large number of initiators have been developed over the years and are known to those skilled in the art. It is possible to conduct radical processes at a variety of temperatures by choosing a suitable initiator (see
Scheme 1 for selected initiators with largely different 10 hours half-life temperatures). However, initiating radical processes at room temperature and below still remains a challenge. It is the purpose of the present invention to provide a safe, general and convenient solution to this problem. - If it is intended to conduct radical processes at room temperature or below, one has to use an initiator that decomposes at such temperatures with a sufficient rate. The desired initiator therefore has to be sufficiently unstable to decompose at relatively low temperature but needs to be stable enough to be produced, transported and handled without requiring extreme precautions. Two examples of such commercially available low temperature initiators are cumyl peroxyneodecanoate and the azobis compound V-70 which have 10 hour half-life temperatures of only 38°C and 30°C, respectively. While these are commercial and useful products, it is evident that such compounds are extremely hazardous, as illustrated by their respective Self Accelerating Decomposition Temperature (SADT) of 10°C and 30°C. Particular care therefore has to be taken during their production, handling and storage.
- To alleviate the inherent safety hazards associated with the use of such unstable compounds, other strategies have been developed in the state of art to generate initiating free radical species at low temperature by external activation of relatively thermally stable compounds. As an example of such strategy, the sensitivity of peroxides and azobis compounds to UV light irradiation has been exploited for initiation purposes in the state of art. However, the quality of commercial solutions can vary and rapidly degrade if not stored under the right conditions. Therefore, finding reliable and robust radical initiation methods for low temperature radical reactions is still highly desirable and it is the purpose of the present invention to provide a safe, general and convenient solution to this problem.
- Peroxyketals are well-known initiators in the context of polymer chemistry, for example in the curing of unsaturated polyester resins, and a variety of them are commercially available.
-
U.S. Patent No. 4,032,596 describes the combination of a perketal and quaternary ammonium salts for the acceleration of the radical curing of polyesters. No acids were used in this invention and the ammonium salt addition was for reducing the curing time at the reaction temperature of around 100°C. - Sheppard and Kamath (Polym. Eng. Sci. 1979, 19, 597) are mentioning the combination of a perketal and dichloroacetic acid for the radical curing of resins. The acid addition was intended for reducing the curing time at the reaction temperature of about 132°C.
-
U.S. Patent No. 4,376,841 describes the combination of geminal bisperoxides (perketals) and an acid or acid-releasing compound for the copolymerization of unsaturated polyester resins to generate undefined crosslinked polymers. - In Schweitzer et al. (Angew. Chem. Int. Ed. 2013, 52, 13228), the combination of a perketal and an acid for the oxidative dimerization of xanthene and the oxidative cross-coupling of xanthene with cyclopentanone is described, but the reaction is limited to forming these two products in medium yields.
- The inventors now found out that free radicals can be easily and reliably generated by the combination of a certain type of organic peroxides and an acid catalyst. These radicals can then initiate radical processes at temperatures well below those needed to induce free radical formation thermally (by homolytic O-O bond cleavage) from these organic peroxides, for example at 0°C.
- In the context of the invention, a free radical is defined, following the IUPAC definition, as a chemical entity having an unpaired electron and is not to be confused with the term radical often used to describe substituents on complex molecules. Similarly, a radical process or reaction is defined as a process or reaction involving or making use of free radicals as reaction intermediates or initiating species. In the rest of this document, an initiator system, or initiator, is to be understood as a chemical compound or combination of chemical compounds capable of generating initiating free radical species under relevant experimental conditions.
- Thus, the present invention is directed to a process for carrying out a chemical radical reaction in which an initiator system capable of generating a radical species for initiating a variety of radical reactions at low temperature is used.
- In more detail, the present invention refers to a process for carrying out a chemical reaction in which a compound capable of forming a chemical radical is reacted with a reaction partner in a radical reaction in the presence of said initiator system comprising at least an acid, preferably selected from a Broensted acid or a Lewis acid, and a compound of the general formula (I) as detailed below.
- Said chemical reactions include, but are not limited to:
- Radical halogenations including the Wohl-Ziegler reaction; including reactions with bromine and chlorine, including reactions with other halide sources like hydrobromic acid N-bromosuccinimide, N-chlorosuccinimide, N-bromophthalimide, N-chlorophthalimide, or N-fluorobenzenesulfonamide; including reactions with substituted hydrocarbon substrates for the formation of benzylic, allylic or aliphatic halides.
- Radical reductions of halides and sulfides; including reactions with aryl halides, alkenyl halides, allylic halides, aliphatic halides, aliphatic aryl sulfides, and with hydrogen sources including tin, germanium and silicon hydride reagents, including tributyl tin hydride, tris(trimethylsilyl)silane, trichlorosilane, poly(methylhydride-siloxane) (PMHS), tertiary thiol or chloroform.
- Radical deoxygenation reactions; including the Barton-McCombie-deoxygenation, including the reaction of a xanthate or xanthic acid ester, a thiocarbonylimidazolyl ester or related dithiocarbonyl compounds with a hydrogen source including tin, germanium and silicon hydride reagents, including tributyl tin hydride, tris(trimethylsilyl)silane, trichlorosilane, diethylsilane, triethylsilane, ethyldimethylsilane, poly(methylhydride-siloxane) (PMHS), tertiary thiol or chloroform, to form the hydrocarbon.
- Radical decarboxylation reactions; including the Barton-decarboxylation; including the reaction of a carboxylic acid derivative, including a thiohydroxamate ester with a hydrogen source including tin, germanium and silicon hydride reagents, including tributyl tin hydride, tris(trimethylsilyl)silane, trichlorosilane, poly(methylhydride-siloxane) (PMHS), tertiary thiol or chloroform, to form the hydrocarbon.
- Radical polymerization reactions including co-polymerization of unsaturated monomers including styrenes, acrylates, methacrylates, acrylonitriles, acrylamides, vinyl acetates; vinyl halides, ethylenes, butadienes, including free-radical polymerization as well as controlled polymerizations following degenerative chain transfer mechanisms, e.g. RAFT or requiring a radical initiator as initiation source, such as for example reverse atom transfer radical polymerization R-ATRP)
- Thiol-ene reactions; including the addition of an alkyl thiol, aryl thiol, thiocarboxylic acid or dithiocarboxylic acid to a C-C multiple bond, including double bond and triple bond, forming sulfides, including aryl-alkyl and dialkyl sulfides, including products additionally containing one or more oxygen atoms like sulfoxides, sulfones or beta-hydroxy, beta-hydroperoxy and beta-keto-sulfides, and including polymers generated by addition of the above mentioned sulfur compounds to suitable unsaturated monomers.
- Radical Addition reactions; including atom transfer radical additions (ATRA), including the reaction of alkyl and aryl halides with compounds containing one or more C-C multiple bonds, including double bonds, aromatic systems (arenes and heteroarenes) and triple bonds, and C-heteroatom multiple bonds, including carbonyl compounds, imines, nitrones, isonitriles, azides and nitriles, resulting in the formal addition of the alkyl and aryl groups, respectively and the halide to the multiple bond, including intramolecular reactions resulting in cyclization.
- Reductive cyclization reactions, including the intramolecular reaction of alkyl and aryl halides with residues containing one or more C-C multiple bonds, including double bonds and triple bonds, and a hydrogen source including tin, germanium and silicon hydride reagents, including tributyl tin hydride, tris(trimethylsilyl)silane, trichlorosilane, poly(methylhydride-siloxane) (PMHS), tertiary thiol or chloroform, resulting in cyclization by the formal addition of the alkyl and aryl groups, respectively, and a hydrogen atom to the multiple bond.
- The initiator system comprises at least two components: a peroxide and an acid catalyst.
-
- X is selected from -OR1, -OC(O)R1, -OC(O)OR1, -OOR1, -NRR1, -SR1, -SSR1,-OP(O)(OR)(OR1), -OP(OR)(OR1), -N3, -NCO, -NCS, -CN, -N3 or halogen; R, R1 and R2 each independently represent H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, acyl, sulfonyl, sulfinyl, phosphonate, phosphinate, silyl, silyloxy, each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent; or
- R1 and R2 form a cyclic 3 to 20 membered ring structure which may further be substituted by alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent or include heteroatoms, including peroxygroup(s), within the cyclic structure;
- R3 is H, alkyl, cycloalkyl, heterocycloalkyl, aryl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl, acyl, sulfonyl, sulfinyl, phosphonyl, phosphinyl, silyl, silyloxyl, each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent;
- R3, R4 and R5 each independently represent H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or a heterosubstituent, or any two of R3, R4 and R5 form a cyclic C2 to C20 hydrocarbon structure which may further be substituted by alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent or include heteroatoms, including peroxygroup(s), within the cyclic structure, and the remaining of R3, R4 and R5 have the meaning as given before.
- The processes as disclosed in
US 4,376,841 making use of geminal bisperoxides for the copolymerization of unsaturated polyester resins to generate crosslinked polymers and the processes of Schweitzer ( Angew. Chem. Int. Ed. 2013, 52, 13228) are not part of the invention. - A heterosubstituent according to the invention is to be understood as a substituent including heteroatoms, preferentially selected from O, N, S, Si and halogens. It can be preferentially selected from, =O, -OH, -F, -Cl, -Br, -I, -CN, -N3, -NO2,-SO3H, NCO, NCS, OP(O)(ORS1)(OR S2), OP(ORS1)(ORS2), a monohalogenomethyl group, a dihalogenomethyl group, a trihalogenomethyl group, -CF(CF3)2, -SF5,-NRS1RS2, -ORS1, -OORS1, -OSiRS1RS3, -OSi(ORS1)RS2RS3,--OSi(ORS1)(ORS2)RS3, -OSi(ORS1)(ORS2)RS3, -OSO2RS1, -SRS1, -SSRS1,-S(O)RS1, -S(O)2RS1, -C(O)ORS1, -C(O)NRS1RS2, -NRS1C(O)RS2, -C(O)-RS1,-COOM, wherein M represents a metal such as Na, K or Cs.
- RS1 RS2 and RS3 each individually represent H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, sulfonyl, silyl, each being optionally substituted by one or more alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl, sulfonyl or heterosubstituent.
- In a further embodiment of the invention, any two of R, R1, R2, R3, R4, R5, RS1 RS2 and RS3 together form a ring structure comprising 3 to 20 ring atoms which may further be substituted by alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent or include heteroatoms, including peroxygroup(s), within the cyclic structure.
- Any one of R1, R2, R3, R4, R5, RS1 RS2 and RS3 may be bound to a soluble polymer or a solid phase material, such as a polymeric or inorganic support.
- In a preferred embodiment, the peroxide component of the general formula (I) comprises at least one peroxyketal group as represented in the general formula (I) wherein X is OOR1 and R1 to R5 have the same meaning as given before.
- For the initiator system in more detail, alkyl may be C1-C20-Alkyl which can be straight chain or branched or cyclic and has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Alkyl might particularly be C1-C6-alkyl, in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, likewise pentyl, 1-, 2- or 3-methylpropyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-, 2-, 3- or 4-methylpentyl, 1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl, 1- or 2-ethylbutyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1,1,2- or 1,2,2-trimethylpropyl. Substituted alkyl groups can be for example trifluoromethyl, pentafluoroethyl and 1,1,1-trifluoroethyl.
- Cycloalkyl may be a cyclic alkyl group forming a 3 to 10 membered ring and might be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
- Heterocycloalkyl may be a cycloalkyl forming a 3 to 10 membered ring and incorporating one or more heteroatoms selected from N, O, S and Si within the cycle. In particular, heterocycloalkyls can be preferentially selected from 2,3-dihydro-2-, -3-, -4- or -5-furyl, 2,5-dihydro-2-, -3-, -4- or -5-furyl, tetrahydro-2- or -3-furyl, 1,3-dioxolan-4-yl, tetrahydro-2- or -3-thienyl, 2,3-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl, 2,5-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl, 1-, 2- or 3-pyrrolidinyl, tetrahydro-1-, -2- or -4-imidazolyl, 2,3-dihydro-1-, -2-, -3-, -4- or -5-pyrazolyl, tetrahydro-1-, -3- or -4-pyrazolyl, 1,4-dihydro-1-, -2-, -3- or -4-pyridyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5- or -6-pyridyl, 1-, 2-, 3- or 4-piperidinyl, 2-, 3- or 4-morpholinyl, tetrahydro-2-, -3- or -4-pyranyl, 1,4-dioxanyl, 1,3-dioxan-2-, -4- or -5-yl, hexahydro-1-, -3- or -4-pyridazinyl, hexahydro-1-, -2-, -4- or -5-pyrimidinyl, 1-, 2- or 3-piperazinyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-quinolyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-isoquinolyl, 2-, 3-, 5-, 6-, 7- or 8-3,4-dihydro-2H-benzo-1,4-oxazinyl.
- Alkenyl might be C2-C20 alkenyl.
- Alkynyl might be C2-C20 alkynyl.
- Halogen is F, Cl, Br or I.
- Aryl might be phenyl, naphthyl or biphenyl and substituted derivatives thereof.
- Aralkyl might be benzyl, naphthylmethyl and substituted derivatives thereof.
- Heteroaryl may have one or more heteroatoms selected from N, O ,S and Si and is preferably 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4-or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, also preferably 1,2,3-triazol-1-, -4- or -5-yl, 1,2,4-triazol-1-, -3- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl, 1,2,3-thiadiazol-4- or -5-yl, 3- or 4-pyridazinyl, pyrazinyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-Indolyl, 4- or 5-isoindolyl, 1-, 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6- or 7-benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1,3-oxadiazolyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl, 5- or 6-quinoxalinyl, 2-, 3-, 5-, 6-, 7- or 8-2H-benzo-1,4-oxazinyl, also preferably 1,3-benzodioxol-5-yl, 1,4-benzodioxan-6-yl, 2,1,3-benzothiadiazol-4- or -5-yl or 2,1,3-benzoxadiazol-5-yl.
- Heteroaralkyl might be any of the aforementioned heteroaryl bound to an alkyl group, such as pyridinylmethyl.
- Optionally substituted means unsubstituted or monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, or even further substituted on the respective group.
-
- Further preferred are
compounds - The peroxide component of the initiator system may be introduced to the reacting system in pure form, as a solution in a solvent, formed in-situ from suitable precursors before the introduction of the acid catalyst component, as an non-purified mixture, for example of components required for its formation under commercially relevant conditions, or be present in residual amounts from a previous process, for example a radical process relying on its thermal decomposition, or as a mixture of several peroxides,
- The acid catalyst component can be any compound with sufficient acidic properties. In particular, the acid catalyst can be an organic or mineral acid, often described as Brønsted acids, or a metal salt with Lewis acidic properties. The acid catalyst component can be used under homogeneous or heterogeneous conditions.
- By homogeneous conditions, it is to be understood that the acid catalyst component is completely or partially soluble in the reaction medium.
- By heterogeneous conditions, it is to be understood that the acid catalyst remains in a separate phase, typically a liquid or solid phase or immobilized on a support, from the reaction medium, allowing for example the recovery of the acid catalyst component at the end of the reaction, while the activation reaction occurs at the interface of these two separate phases.
- In a preferred embodiment, the acid catalyst can be an organic or mineral acid having a pKa value in water of 4,75 or lower. Such acid might be for example trifluoroacetic acid, nitric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, para-toluenesulfonic acid, phosphoric acid, trifluoromethanesulfonic acid (triflic acid), 1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (triflimide).
- In another preferred embodiment, the acid catalyst can be a salt of an element selected from
groups 1, 2, 3, 4, 12, 13, 14 and 15 of the periodic table. Such acid catalyst might be for example Scandium(III) triflate, Ytterbium(III) triflate, Titanium(IV) chloride, Hafnium(III) triflate, Zinc(II) chloride, Aluminium(III) chloride, Indium(III) triflate, Tin(II) chloride, Tin(IV) chloride, Bismuth(III) triflate. - In the inventive process, mixtures of peroxides having different reactivities and/or mixtures of acids having different pKa value can be used in order to control the free radical reaction.
- The ratio of peroxide to acid catalyst components can vary widely from 1:100 to 100:1 depending on the particular radical process in which it is to be used.
- Preferably, the ratio varies between 1:10 to 10:1. Typically, a 1:1 ratio is advantageously convenient.
- The amount of initiator can again widely vary depending on the particular radical process being initiated. Preferred amounts can vary from catalytic amounts, for example from 0.01 mol% to 20 mol% to overstoichiometric amounts, as high as 1000 mol%.
- The inventive initiator system is compatible with a wide variety of inert or reactive solvents. Therefore, solvents used in the inventive process are not particularly limited or even required and may be preferably selected from aliphatic, cycloaliphatic or aromatic solvents, chlorinated solvents, alcohols, in particular lower aliphatic alcohols, esters, ethers or mixtures thereof such as, for example, hexane, benzene, toluene, dichloromethane, chloroform, methanol, dimethylsulfoxide, acetic acid, acetonitrile, ethyl acetate or diethyl ether. The initiator system can also be used without any additional solvent, for example in the case of a radical polymerisation.
- The reaction temperature is in general a temperature lower than the 10 hour half-life temperature of the peroxide component of general Formula (I) used. It can therefore be generally selected from any temperature below 100°C. In a preferred embodiment, the temperature is selected between -40°C and 60°C. Typically, reactions are advantageously run between 0°C and 25°C.
- As assumed by the inventors and shown in Scheme 3, the radicals are formed from the peroxide component (24) in the presence of an acid catalyst component by the formation of an alkenyl peroxide (25), which is a generally very unstable structure that rapidly decomposes into radical (26) and an oxyl radical by O-O bond homolysis at low temperatures.
- The so-generated free radicals can then be used as initiating species for many types of radical process known to those skilled in the art, including, for example, but not limited to, all as further exemplified above:
- Radical halogenations including the Wohl-Ziegler reaction;
- Radical reductions of halides ;
- Radical deoxygenation reactions;
- Reductive cyclization reactions;
- Radical polymerization reactions including co-polymerization of unsaturated monomers including styrenes, acrylates, methacrylates, acrylonitriles, acrylamides, vinyl acetates; vinyl halides, ethylenes, butadienes, including free-radical polymerization as well as controlled polymerizations following degenerative chain transfer mechanisms, e.g. RAFT or requiring a radical initiator as initiation source, such as for example reverse atom transfer radical polymerization R-ATRP)
- Thiol-ene reactions.
- Radical Addition reactions.
- The examples detailed by the inventors below only serve to demonstrate the generality and utility of the initiator system for the processes described in the present invention. It is however to be understood that these examples serve only for illustration purposes and do not limit the breadth of applications covered by the present invention. Those skilled in the art will easily recognize the potential of the present invention to be used for the initiation of a variety of other radical processes at low temperature not described by the inventors in the following examples. Such radical processes are for example radical deoxygenations, known as the Barton-McCombie reaction; polymerisation of a wide variety of olefinic monomers, such as vinyl acetates, acrylonitriles, butadiene and the like; or the wide variety of radical chain reactions relying on metal-hydride, such as tin, germanium or silicon hydrides, or sulphur based radical transfer agents.
- According to the invention, the peroxides which can be used according to the invention are not particularly limited as long as they are covered by the formula (I) as represented above. Compounds that have been exemplarily used by the inventors are peroxides 1-11b, shown in Scheme 2. Some of these compounds as well as derivatives thereof are commercially available.
- Thus, the inventive initiator system can be particularly used as a complementary strategy to the existing radical initiators. Said initiator system can be used to efficiently initiate radical processes at ambient temperature, temperatures as low as -20°C or even lower. This combination has the potential to become an extremely useful and widely used system, given the commercial availability of several peroxides, their tolerance to air and moisture, their high thermal stability, compared to specifically designed low temperature initiators, and the extreme simplicity of the experimental procedure.
- The introduction of an activation catalyst as found by the inventors offers the opportunity to finely tune the rate of formation of free radicals from a specific peroxide based on the nature or the concentration of the acid component. It therefore presents an attractive alternative to the use of syringe pump techniques that are often used in the context of organic synthesis to keep the concentration of initiating free radicals low.
- The invention is further illustrated by the following Examples.
-
- All reactions were performed according to the following procedure: In an oven-dried Schlenk flask fluorene 27 (83 mg, 0.5 mmol, 1 eq) and N-bromosuccinimide (98 mg, 0.55 mmol, 1.1 eq) were dissolved in dichloromethane (5 mL). The desired peroxide (0.025 mmol, 5 mol %) was introduced and the resulting mixture was degassed by the freeze-pump-thaw method (3 cycles). After warming to room temperature, the acid catalyst was added under a stream of argon and after the desired reaction time, the reaction mixture was quenched with NEt3 (250 µL), CH2Br2 (0.5 mmol) was added as a standard for analytical purposes only and an aliquot taken for direct 1H NMR analysis. Yield was determined by integrating a reference peak of 28 (5.9 ppm, s, 1 H; determined from an authentic sample) relative to the peak of CH2Br2. The results of the reactions are detailed in (Table 1).
Table 1: Wohl-Ziegler bromination of fluorene at room temperature. Entry Peroxide Acid catalyst Yield of 28 (%) 1 1 H2SO4 72 2 1 pTsOH 67 3 1 CH3SO3H 45 4 1 HNO3 96 5 1 CF3CO2H 22 6 1 CCl3CO2H 18 7 1 AcOH 0 8 1 Sc(OTf)3 69[a] 9 11b CH3SO3H 21 10 11a CH3SO3H 47 11 2 CH3SO3H 10; 76[b] 12 5 CH3SO3H 20 13 6 CH3SO3 H 0; 33[b] 14 7 CH3SO3 H 0; 9[b] 15 3 CH3SO3 H 0; 8[b] 16 4 CH3SO3 H 1; 12[b] 17 9 CH3SO3H 50 18 10 CH3SO3H 74 [a] reaction performed in acetonitrile as solvent; [b]After 72 hours of reaction - The bromination proceeded efficiently using a commercial solution of peroxyketal 1 (
Trigonox® 22, 50% weight in mineral oil) in combination with different Brønsted acids. Control experiments confirmed the requirement for both acid and peroxide, no conversion being observed after 24 hours if either one of these components was omitted. A clear trend following the pK a value of the acid catalyst can be seen: stronger acids give faster conversion. - Sulfuric and para-toluene sulfonic acid have similar behaviour with 72% and 67% of 28 after one hour, respectively (
entries 1 and 2). Methane sulfonic acid gave a slightly lower yield (45%; entry 3) while acids weaker than trifluoroacetic acid (22%, entry 5) or trichloroacetic acid (18%, entry 6) failed to give any conversion (entry 7). Nitric acid is more efficient than its pK a value would suggest (96%; entry 4). Eventually, all reactions gave high yields when allowed to reach full conversion (80-95% yield of 28 after 24 to 72 hours), showing that the acid catalyst only influences the initiation rate. Scandium (III) triflate, a Lewis acid, was also found to be competent (69%; entry 8). - Different commercial peroxyketal solutions were evaluated using methane sulfonic acid as a standard catalyst of medium reactivity. 2 (Trigonox® D; 50% weight) proved to be less efficient than 1 (45%, entry 3), giving 10% of product 28 after one hour and 76% after 48 hours (entry 11). 3 (Trigonox® 301; 41% weight) showed low conversion after two days of reaction (8%, entry 15). 4 (Luperox® DHD-9, 32% weight) was found to be slightly more reactive than 3, giving 12% product after 48 hours (entry 16).
- Based on the observation of this strong influence of the peroxyketal structure on its reactivity, the inventors evaluated a series of structurally different peroxides. The effect of the group X of Formula (I) is shown by compounds 11a and 11b. 11b proved to be less reactive than 1 (21%, entry 9) while 11a was more efficient, giving 47% of 28 after one hour (entry 10). Aromatic substituents around the peroxide moiety can have significant effects: 5 is more effective than 2 (20%, entry 12 compared to entry 11), while 6 was much less efficient (33% after 48 h, entry 13) 9 was found to be slightly more reactive than 1 (50%, entry 17) while 10 was the most efficient of the structures evaluated, giving 74% of 28 after one hour of reaction (entry 18).
-
- Performing the reaction at -10°C, using a stoichiometric amount of 1 and methane sulfonic acid, a 60% yield of 28 was obtained after 24 hours., With
peroxide 10, the reaction could be performed successfully at -20°C, giving 25% of product 28 after 24 hours (Scheme 6). These results show that the efficiency of the initiation system can be improved by the right selection and combination of peroxide component and acid catalyst component and tuned for specific applications wherein fast or slow initiation rates or the use of cryogenic temperatures are required. - Bulk polymerization of methyl methacrylate (MMA) was performed using the inventive initiator system at room temperature by the following procedure.
- All tests were performed under air by dissolving the corresponding peroxide solution (10 µL, 1 vol %) in 1 mL of MMA (containing 1 mg.mL-1 of 9-nitronanthracene as colorant for better visualization) and adding methane sulfonic acid (5 µL, 0.5 vol %). The vial was left to stand until a glass-like solid was obtained. Full polymerization was considered achieved when a solid glass-like solid was obtained with low residual monomer odor. The times required for full polymerization are summarized in Table 2.
Table 2: Bulk Polymerisation of MMA at Room Temperature. Entry Peroxide Additive Time (h) 1 1 - 6 2 2 - 22 3 3 - 70 4 4 - 46 5 1 MeOH (10 µL) 9 6 2 MeOH (10 µL) 50 7 3 MeOH (10 µL) 70 8 4 MeOH (10 µL) 22 - All peroxide components evaluated successfully initiated the polymerization of MMA at room temperature in varying amounts of time. The observed order of reactivity of peroxide components is 1 (6 hours, entry 1) > 2 (22 hours, entry 2) > 4 (46 hours, entry 4) > 3 (70 hours, entry 3), as expected from the results of Example 1.
- The presence of small amounts of methanol as additive slowed the polymerisation of MMA with
peroxides 1 and 2 (6h,entry 1 Vs 9h, entry 5 for 1; 22h (entry 2 Vs 50h, entry 6 for 2) but accelerated it for peroxide 4 (46h, entry 3 Vs 22h, entry 8). - Examples for radical polymerization reactions that have been conducted making use of the inventive initiator system include the synthesis of poly(n-butyl acrylate), poly(n-butyl acrylate)-b-poly(t-butyl acrylate) (a block copolymer), poly(styrene) and poly(N-isopropylacrylamide). These reactions have been carried out at ambient temperature and 0°C, respectively. These polymers have been synthesized with and without the technique of reversible addition fragmentation transfer (RAFT) polymerization.
-
Peroxide 1 can be efficiently used to initiate radical polymerizations when being combined with a Brønsted acid at low temperature with any radically polymerizable vinyl monomer, such as for example styrene, butyl acrylate or N-isopropyl acrylamide. Polymers of high molecular weight are obtained in uncontrolled radical polymerizations in accordance with general expectations of such reactions. Initiation pathways have been identified and the initiating moieties do not correspond to a thermal decay of 1, but to the fragments as outlined in Scheme 4. Furthermore, 1 combined with an acid (e.g. trifluoroacetic acid) can be used to initiate also room temperature degenerative transfer polymerizations, i.e. reversible addition fragmentation radical transfer polymerization (RAFT). Good control over a series of polymerizations is achievable, also allowing for block copolymer synthesis. Polymers show low dispersities (1.1-1.3) and the average degree of polymerization increases linearly with increasing monomer conversion. A good end-group functionality is detected via soft-ionization mass spectrometry. The evolution of number-average molecular weight of poly(n-butyl acrylate) with increasing monomer conversion obtained from room temperature RAFT polymerization employing 1 is illustrated inFigure 1 . - A typical experimental procedure for polymerisation is as follows:
- 10 mmol (20 equiv) of monomer, 0.5 mmol (1 equiv) of DoPAT RAFT agent, when applicable, and 0.5 mmol (1 equiv) of 1 were added into a sealed glass vial containing a stirring bar which was purged with nitrogen for 10 min and subsequently inserted in a glovebox under inert atmosphere. The reaction was started by adding 0.025 mmol (0.05 equiv.) of para-toluene sulfonic acid, dissolved in 0.1 mL of acetonitrile. The mixture was polymerized at the desired temperature inside the glove-box. Samples were taken and quenched with hydroquinone/methanol after specific reaction times to determine conversion (by NMR) and molar mass (by SEC). After 24 hours, the residual reaction mixture was quenched by adding a solution of hydroquinone (1 mmol, 2 equiv) in methanol and poured into an aluminium pan to evaporate any residual monomer and solvent. Molar mass distribution and end group fidelity were determined by THF-SEC and ESI-MS analysis.
-
- In an oven dried Schlenk tube, tBuSH (225µL, 2 mmol), 4-phenyl butane (75µL, 0.5 mmol) and 1 (50% solution, 52 mg, 0.1 mmol) were dissolved in acetonitrile (5 mL). The resulting mixture was degassed (Freeze-Pump-Thaw technique, 3 cycles), brought to room temperature and methane sulfonic acid (3.5 µL, 0.05 mmol) was added and the mixture left to react overnight. The mixture was transferred to an extraction funnel, diluted with ethyl acetate (20 mL) and washed with NaOH (2M,
2x 10 mL) and distilled water (2x 10 mL). The organic phase was dried over Na2SO4, evaporated to dryness and the resulting oil was purified by flash chromatography on silica gel (Hex/AcOEt 99:1 as eluent) to afford 29 as a clear oil (98mg, 88% yield). -
- In an oven dried Schlenk tube, CCl4 (962µL, 10 mmol), 4-phenyl butane (150µL, 1 mmol) and 1 (50% solution, 260 mg, 0.5 mmol) were dissolved in acetonitrile (1 mL). The resulting mixture was degassed (Freeze-Pump-Thaw technique, 3 cycles), brought to room temperature and methane sulfonic acid (7 µL, 0.1 mmol) was added and the mixture left to react overnight. The mixture was evaporated to dryness and the resulting oil was purified by flash chromatography on silica gel (hexane as eluent) to afford 30 as a clear oil (175 mg, 61% yield).
-
- In an oven dried Schlenk tube, 9-iodophenanthrene (304 mg, 1 mmol), was dissolved in dichloromethane (10 mL). The resulting solution was degassed (Freeze-Pump-Thaw technique, 3 cycles), brought to room temperature and 1 (50% solution, 26 mg, 0.05 mmol) and TMS3SiH (308 µL, 1 mmol) were added.
- The mixture was degassed once more and after being brought back to room temperature, methane sulfonic acid (3.5 µL, 0.05 mmol) was added and the mixture left to react for 30 minutes. The mixture was evaporated to dryness and the resulting slightly yellow oil was purified by flash chromatography on silica gel (hexane as eluent) to afford 31 as a white solid (168 mg, 94% yield).
-
- In an oven dried Schlenk tube, 32 (259 mg, 1 mmol), was dissolved in dichloromethane (10 mL). The resulting solution was degassed (Freeze-Pump-Thaw technique, 3 cycles), brought to room temperature and 1 (50% solution, 26 mg, 0.05 mmol) and TMS3SiH (308 µL, 1 mmol) were added. The mixture was degassed once more and after being brought back to room temperature, methane sulfonic acid (3.5 µL, 0.05 mmol) was added and the mixture left to react for 2 hours. The mixture was evaporated to dryness and the resulting slightly yellow oil was purified by flash chromatography on silica gel (pentane as eluent) to afford 33 as a clear oil (106 mg, 79% yield)
- These different examples demonstrate the generality of the inventive initiator system for low temperature radical processes, including cryogenic conditions. Abstraction of a hydrogen atom from suitable substrates is possible, as shown by the success of the Wohl-Ziegler and thiol-ene reactions. Direct abstraction of halogen atoms, presumably by the complementary carbon centred radical formed, is also possible, as in the ATRA of CCl4. If the radicals generated are not reactive enough to initiate chains themselves, they are competent in initiating reactions relying on the use of a hydride mediator like TMS3SiH. Besides these examples oriented towards organic synthesis, radical polymerization of several olefin monomers is successfully initiated at room temperature and below. The present invention could therefore be extremely valuable for applications where low temperatures are required.
- The present invention offers a cheap, safe and user-friendly alternative to the low temperature radical initiators currently known.
Claims (15)
- Process for carrying out a chemical reaction in which a compound capable of forming a chemical radical is reacted with a reaction partner at a temperature of below 100°C in a radical reaction in the presence of reaction pair of an acid, preferably selected from a Broensted acid or a Lewis acid, and of a compound of the general formula (I):X is selected from -OR1, -OC(O)R1, -OC(O)OR1, -OOR1, -NRR1,-SR1, -SSR1, -OP(O)(OR)(OR1), -OP(OR)(OR1), -N3, -NCO, -NCS, -CN, -N3 or halogen;R, R1 and R2 each independently represent H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, acyl, sulfonyl, sulfinyl, phosphonate, phosphinate, silyl, silyloxy, each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent; orR1 and R2 form a cyclic 3 to 20 membered ring structure which may further be substituted by alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent or include heteroatoms, including peroxygroup(s), within the cyclic structure;R3 is H, alkyl, cycloalkyl, heterocycloalkyl, aryl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl, acyl, sulfonyl, sulfinyl, phosphonyl, phosphinyl, silyl, silyloxyl, each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent;R3, R4 and R5 each independently represent H, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or a heterosubstituent, or any two of R3, R4 and R5 form a cyclic C2 to C20 hydrocarbon structure which may further be substituted by alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterosubstituent groups; each being optionally substituted by one or more groups selected from alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, heteroaryl, aralkyl, heteroaralkyl or heterosubstituent or include heteroatoms, including peroxygroup(s), within the cyclic structure, and the remaining of R3, R4 andR5 have the meaning as given before.
- Process according to claim 1, wherein the peroxide compound is represented by the general formula (I) wherein X is OOR1 and R1 to R5 have the meaning as defined in claim 1.
- Process according to any of claims 1 to 3, wherein the acid component is an organic or mineral acid or a metal salt with Lewis acidic properties.
- Process according to any of claims 1 to 4, wherein the acid catalyst is an organic or mineral acid having a pKa in water of 4,75 or lower.
- Process according to any of claims 1 to 5 wherein the acid catalyst is selected from trifluoroacetic acid, nitric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, para-toluenesulfonic acid, phosphoric acid, trifluoromethanesulfonic acid (triflic acid), 1,1,1-trifluoro-N-((trifluoromethyl)sulfonyl)methanesulfonamide (triflimide).
- Process according to any of claims 1 to 3, wherein the acid catalyst is a salt of an element selected from group 1, 2, 3, 4, 12, 13, 14 and 15 of the Periodic Table.
- Process according to claim 7, wherein the acid catalyst is selected from Scandium(III) triflate, Ytterbium(III) triflate, Titanium(IV) chloride, Hafnium(III) triflate, Zinc(II) chloride, Aluminium(III) chloride, Indium(III) triflate, Tin(II) chloride, Tin(IV) chloride, Bismuth(III) triflate.
- Process according to any of claims 1 to 8 wherein the peroxide component of general formula (I) and the acid component are used in a ratio from 1:100 to 100:1, preferably in a ratio between 1:5 to 5:1.
- Process according to any of claims 1 to 9, wherein the peroxide component of general formula (I) is used in pure form, as a solution in a solvent, formed in-situ from suitable precursors before the introduction of the acid catalyst component, as an unpurified mixture of components required for its formation.
- Process according to any of claims 1 to 10, wherein the acid catalyst component is used under homogeneous conditions such that it is completely or partially soluble in the reaction medium.
- Process according to any of claims 1 to 10, wherein the acid catalyst component is used under heterogeneous conditions in a separate liquid or solid phase or immobilized on a support.
- Process according to any of claims 1 to 12, wherein the radical reaction is selected from the group comprising of:• Radical halogenations including the Wohl-Ziegler reaction;• Radical reductions of halides ;• Radical deoxygenation reactions;• Reductive cyclization reactions;• Radical polymerization reactions including co-polymerization of unsaturated monomers including styrenes, acrylates, methacrylates, acrylonitriles, acrylamides, vinyl acetates; vinyl halides, ethylenes, butadienes, including free-radical polymerization as well as controlled polymerizations following degenerative chain transfer mechanisms, including RAFT or requiring a radical initiator as initiation source, including reverse atom transfer radical polymerization R-ATRP);• Thiol-ene reactions;• Radical addition reactions;each reaction carried out at temperatures below 100°C and preferably below 40°C.
- Use of the initiator system of claim 14 in radical-initiated reactions wherein the radical reaction is selected from the group comprising of:• Radical halogenations including the Wohl-Ziegler reaction;• Radical reductions of halides ;• Radical deoxygenation reactions;• Reductive cyclization reactions;• Radical polymerization reactions including co-polymerization of unsaturated monomers including styrenes, acrylates, methacrylates, acrylonitriles, acrylamides, vinyl acetates; vinyl halides, ethylenes, butadienes, including free-radical polymerization as well as controlled polymerizations following degenerative chain transfer mechanisms, e.g. RAFT or requiring a radical initiator as initiation source, such as for example reverse atom transfer radical polymerization R-ATRP)• Thiol-ene reactions;• Radical addition reactions.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15202134.1A EP3184508A1 (en) | 2015-12-22 | 2015-12-22 | Low temperature radical initiator system and processes making use thereof |
EP16820239.8A EP3394029A1 (en) | 2015-12-22 | 2016-12-20 | Low temperature radical initiator system and processes making use thereof |
SG11201804698QA SG11201804698QA (en) | 2015-12-22 | 2016-12-20 | Low temperature radical initiator system and processes making use thereof |
PCT/EP2016/081883 WO2017108761A1 (en) | 2015-12-22 | 2016-12-20 | Low temperature radical initiator system and processes making use thereof |
JP2018533789A JP2019507112A (en) | 2015-12-22 | 2016-12-20 | Low temperature radical initiator system and method of use thereof |
US16/065,176 US20180371144A1 (en) | 2015-12-22 | 2016-12-20 | Low temperature radical initiator system and processes making use thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15202134.1A EP3184508A1 (en) | 2015-12-22 | 2015-12-22 | Low temperature radical initiator system and processes making use thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3184508A1 true EP3184508A1 (en) | 2017-06-28 |
Family
ID=55236129
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15202134.1A Withdrawn EP3184508A1 (en) | 2015-12-22 | 2015-12-22 | Low temperature radical initiator system and processes making use thereof |
EP16820239.8A Withdrawn EP3394029A1 (en) | 2015-12-22 | 2016-12-20 | Low temperature radical initiator system and processes making use thereof |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16820239.8A Withdrawn EP3394029A1 (en) | 2015-12-22 | 2016-12-20 | Low temperature radical initiator system and processes making use thereof |
Country Status (5)
Country | Link |
---|---|
US (1) | US20180371144A1 (en) |
EP (2) | EP3184508A1 (en) |
JP (1) | JP2019507112A (en) |
SG (1) | SG11201804698QA (en) |
WO (1) | WO2017108761A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3090640A1 (en) * | 2018-12-21 | 2020-06-26 | Arkema France | Use of at least one hemi-peroxyacetal, alone or in combination with other peroxides, to initiate the polymerization or copolymerization of ethylene under high pressure |
WO2021123692A1 (en) * | 2019-12-18 | 2021-06-24 | Arkema France | Composition comprising a hemiperoxyacetal, method for polymerizing same, use thereof, and composition material obtained upon polymerization of the composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4032596A (en) | 1976-10-20 | 1977-06-28 | Air Products And Chemicals, Inc. | Cure accelerators for peroxyketal initated polyester resins |
US4376841A (en) | 1976-04-26 | 1983-03-15 | Akzona Incorporated | Copolymerization of unsaturated polyester resins |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016040802A1 (en) * | 2014-09-12 | 2016-03-17 | Ashland Licensing And Intellectual Property Llc | Compositions comprising curable resin for anti-static flooring |
-
2015
- 2015-12-22 EP EP15202134.1A patent/EP3184508A1/en not_active Withdrawn
-
2016
- 2016-12-20 US US16/065,176 patent/US20180371144A1/en not_active Abandoned
- 2016-12-20 JP JP2018533789A patent/JP2019507112A/en active Pending
- 2016-12-20 SG SG11201804698QA patent/SG11201804698QA/en unknown
- 2016-12-20 EP EP16820239.8A patent/EP3394029A1/en not_active Withdrawn
- 2016-12-20 WO PCT/EP2016/081883 patent/WO2017108761A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4376841A (en) | 1976-04-26 | 1983-03-15 | Akzona Incorporated | Copolymerization of unsaturated polyester resins |
US4032596A (en) | 1976-10-20 | 1977-06-28 | Air Products And Chemicals, Inc. | Cure accelerators for peroxyketal initated polyester resins |
Non-Patent Citations (4)
Title |
---|
LAIEVEE, J.; FOUASSIER, J. P.: "Encyclopedia of Radicals in Chemistry, Biology and Materials", 2012, article "Overview of Radical Initiation" |
SCHWEITZER ET AL., ANGEW. CHEM. INT. ED., vol. 52, 2013, pages 13228 |
SCHWEITZER, ANGEW. CHEM. INT. ED., vol. 52, 2013, pages 13228 |
SHEPPARD; KAMATH, POLYM. ENG. SCI., vol. 19, 1979, pages 597 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3090640A1 (en) * | 2018-12-21 | 2020-06-26 | Arkema France | Use of at least one hemi-peroxyacetal, alone or in combination with other peroxides, to initiate the polymerization or copolymerization of ethylene under high pressure |
WO2020128328A3 (en) * | 2018-12-21 | 2020-08-20 | Arkema France | Use of at least one hemo-peroxyacetal, alone or in combination with other peroxides, to promote polymerisation or copolymerisation of ethylene under high pressure |
WO2021123692A1 (en) * | 2019-12-18 | 2021-06-24 | Arkema France | Composition comprising a hemiperoxyacetal, method for polymerizing same, use thereof, and composition material obtained upon polymerization of the composition |
FR3105228A1 (en) * | 2019-12-18 | 2021-06-25 | Arkema France | COMPOSITION INCLUDING A HEMIPEROXYACETAL, ITS POLYMERIZATION PROCESS, ITS USE AND COMPOSITION MATERIAL OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION |
Also Published As
Publication number | Publication date |
---|---|
SG11201804698QA (en) | 2018-07-30 |
WO2017108761A1 (en) | 2017-06-29 |
JP2019507112A (en) | 2019-03-14 |
EP3394029A1 (en) | 2018-10-31 |
US20180371144A1 (en) | 2018-12-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2231398C (en) | Control of molecular weight and end-group functionality in polymers | |
Houshyar et al. | The scope for synthesis of macro-RAFT agents by sequential insertion of single monomer units | |
AU770550B2 (en) | Synthesis of dithioester chain transfer agents and use of bis(thioacyl) disulfides or dithioesters as chain transfer agents | |
EP1399488B1 (en) | Improved heterocycle containing control agents for living-type free radical polymerization | |
KR100420093B1 (en) | Synthesis of Terminally Unsaturated Oligomers | |
EP2604633B1 (en) | Manufacturing method of (meth) acrylic polymer | |
JP2005320549A (en) | Free radical polymerization process | |
US20020065380A1 (en) | Emulsion living-type free radical polymerization, methods and products of same | |
KR100638540B1 (en) | Process for the preparation of polyalkoxyamines which can be used as initiators for the radical polymerization of polyfunctional living copolymers | |
FR2843394A1 (en) | New alkoxy-amine compounds derived from beta-phosphorylated nitroxide compounds, used as initiators for the polymerization of radically-polymerizable monomers | |
EP3184508A1 (en) | Low temperature radical initiator system and processes making use thereof | |
KR101442001B1 (en) | Method for producing polar group-containing olefin copolymers | |
US4696987A (en) | Process for the preparation of polymers of vinylphosphonic acid in protic solvents | |
FR2552434A1 (en) | PROCESS FOR THE PRODUCTION OF SILANE FROM METHYLDICHLOROSILANE AND CHLOROSILANES | |
US6667376B2 (en) | Control agents for living-type free radical polymerization and methods of polymerizing | |
KR20170068475A (en) | Using organic photoredox catalysts to achieve metal free photoregulated controlled radical polymerization | |
WO1991007387A1 (en) | Allyl peroxide chain transfer agents | |
CN109071408B (en) | Method for producing alpha-fluorinated acrylate | |
JP2017061422A (en) | High-purity para-styrene sulfonic acid ester, and method for producing thereof | |
US20060160774A1 (en) | Oxathiazaphospholidine free radical control agent | |
Lockley et al. | Cyclic diperoxides as sources of radicals for the initiation of the radical polymerization of methyl methacrylate | |
EP0672070A1 (en) | Process for molecular weight regulation in (co)polymers | |
KR100470238B1 (en) | A catalyst having high catalytic activity for the preparation of polystyrene | |
US3586722A (en) | Sulfonyl peroxides | |
AU720690B2 (en) | Control of molecular weight and end-group functionality in polymers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20180103 |